Phosphonocarboxylic acid amides

ABSTRACT

PHOSPHONCARBOXYLIC ACID AMINDES OF THE FORMULA   R1-O-P(=X)(-O-R2)-CNH2N-CO-NH-CH(-C(-CL)3)-NH-A   ARE PROVIDED, WHEREIN R1 AND R2 EACH DENOTE AN ALKYL HALOGENOALKYL OR ALKENYL RADICAL WITH AT MOST 4 CARBON ATOMS, A DENOTES AN OPTIONALLY FURTHER SUBSTITUTED ARYL OR ALKYL RADICAL, X DENOTES A SULPHUR OR AN OXYGEN ATOM AND N IS AN INTEGER OF 1 TO 3. THESE COMPOUNDS ARE USEFUL FOR FLAMEPROOFING OF PLASTICS OR CASTING COMPOSITIONS WHICH SERVE FOR THE MANUFACTURE OF SHAPED ARTICLES, SUCH AS FOAMS, FILMS OR FIBERS.

United States Patent ice .3323;

stituted further, a benzene radical which contains one or 3,773,860 more substituents, such as methyl groups, ethyl groups PHOSPHONOCAR'BOXYLIC ACID AMIDES and/or chlorine atoms, a butyl, isopropyl, ethyl or methyl Hermann Nachbur Dornach and Arthur Maeder 'Therrou hl wil, Switzerland: assignors to Ciba-Geigy AG, Basel, g or a c oroethyl group The aryl radical A can Switzefland 5 furthermore also represent a benzene radical or especially No Drawing. Filed Aug. 5, 1911, Ser. No. 169,493 f fii g g rfadlcal Whwh Pmsesses, as subsum- Claims priority, application Switzerland, Aug. 7, 1970, en e rmu1a Int. Cl: C07f 9/40 US. Cl. 260-943 7 Claims 10 (4) X ABSTRACT OF THE DISCLOSURE Phosphonocarboxylic acid amides of the formula Q13 B -O X 15 Rr-O CnHznCONHCHNHA wherein R R X and n have the indicated meaning. Par- 1301s ticularly suitable phosphonocarboxylic acid amides are those which terminal] at the --NH rou ossess a are PIOVlded, Whereln 1 R2 F denote an alkyl benzene radical which is further substitu ted y an alkyl halogenoalkyl alkeny} radlcal at 4 carbon group such as methyl, or a halogen atom such as chlorine, atoms A denotes an optlonauy further Subsmuted aryl or or above all a benzene radical which is not substituted 53 fafilcalr X denotes a sulphur an oxygen atom and further, for example the phosphonocarboxylic acid amides n is an integer of 1 to 3. These compounds are useful for of the f l fiameproofing of plastics or casting compositions which serve for the manufacture of shaped articles, such as foams, films or fibres. (5) Rho O The subject of the invention are phosphonocarboxylic z acid amides of the formula RPO CHPOH CO NH CH NH@ Ca (1) R1 O\ //X P Rr-O coHz -CO-NHCHNHA n wherein R has the indicated meaning and Z denotes as hydrogen atom, a chlorine atom or a methyl group.

wherein R and R each denote an alkyl, halogenoalkyl or The phosphonocarboxylic acid amides of the Formulae alkenyl radical with at most 4 carbon atoms, A denotes 1 to 3 and 5 can be obtained in a manner which is in itan aryl or alkyl radical which is optionally substituted 40 self known, from phosphonopropionic acid ot-hydroxyfurther, X denotes a sulphur atom or preferably an oxy- B,/8,fl-trichloroethylamides and isocyanates, in accordance gen atom and n denotes an integer having a value of 1 with the equation. to 3.

Phosphonocarboxylic acid amides of the formula (2) R -o X [-Arlnn 0 0-Rr 1 Rr-O CnHinCO-NH-CHNH --A2-NHCHNHCOCnH2n O-Ra Ch Ch 2-m wherein R R X and it having the indicated meaning, X

A denotes a benzene radical which is optionally substi- OH 0 tuted by methyl, ethyl or chlorine, or denotes alkyl with 4: g at most 4 carbon atoms, A denotes phenylene or diphen- Rn-O C..Hr..-CO-NH H =N-A ylmethane and m denotes 1 or 2, are of particular interest. (6.1) (6.2)

Amongst these, the phosphonocarboxyhc acid amides x which correspond to the formula 1 y P (3) Ra-O X m-o CnHrnCONHCHNH-A co,

to. Rr-O OHa-CH-CONHCH-NH-As wherein R denotes a methyl, ethyl, chloroethyl or allyl Here 1 2 and again have t indicated meaninggroup, A denotes a benzene radical, an alkyl group with The reaction 15 pp p y earned out l modfifately at most 4 carbon atoms or a halogenoalkyl group with at elevated temperature, 111 t p e of an n t t, most 4 carbon atoms and Y denotes a hydrogen, atom or Such as dimethylfofmamlder and 118mg at least PP a methyl group, are preferred, R here preferably r mately equivalent amounts of the two starting substances, resents a methyl or ethyl group, and Y represents a hyoptionally with the addition of a catalyst. Where comdrogen atom. pounds of the Formula 2, wherein m is 1', are manufac- The radical A, or A A or A can be, for example, tured, about 1 mol of diisocyanate is, of course, reacted a naphthalene radical or benzene radical which is not subwith about 2 mols of phosphonocarboxylic acid amide.

The compounds thus obtainable can in general be isolated easily by distilling ofl? the solvent, and can be purified by recrystallisation.

The amides of the Formula 4 required as starting substances are obtained by reaction of acid amides, containing an unsubstituted acid amide group, with chloral hydrate:

This reaction, again, is advantageously carried out at elevated temperature, for example 50 to 150 C., using equivalent amounts of the starting substances, and in the presence of an inert solvent. Possible inert solvents are, for example, aromatic hydrocarbons such as xylenes, toluene or especially benzene. Appropriately, the reaction is allowed to take place at 70 to 120 C., advantageously at the boiling point of the reaction mixture, and the water of reaction is removed continuously.

The phosphonocarboxylic acid amides of the Formulae 1, 2, 3 and 5 can be used as flameproofing agents. In this case they can, for example, be fixed from aqueous dispersion onto textile materials, for example cellulose fibres, with the aid of a so-called pigment fixing agent. They can also be used from organic solvents, such as dirnethylformamide, trichloroethylene or perchloroethylene.

Preferably, however, they are incorporated into plastics or casting compositions which are to serve for the manufacture of shaped articles, such as foams, films or especially fibres. Regenerated cellulose, polyamides, polyesters, polyurethanes, polyalkylenes and polyacrylonitrile may be mentioned as examples of such compositions.

However, particularly advantageous results are obtained if phosphonocarboxylic acid amides of the Formula 1 are incorporated into viscose compositions which are then further processed into films or preferably into fibres. It is advisable first to convert the phosphonocarboxylic acid amides into aqueous dispersions of fine particle size by means of suitable surface-active agents, and to incorporate them in this form into the viscose composition. The content of phosphonocarboxylic acid amide, relative to pure cellulose, is preferably 20 to 50%, for example 25 to 40%.

The other preferred use is the use as a flameproofing agent for polyurethanes.

The compounds of the Formula 1 are appropriately incorporated into the polyurethane foams or polyurethane coatings by adding them to the mixture used for the manufacture of the foams or to the coating compositions.

These manufacturing mixtures have the usual composition for the manufacture of polyurethane foam. As a rule, they contain polyethers with free hydroxy groups, for example polyols, and diisocyanates such as, for example, 4,4'-diphenylmethane-diisocyanate or toluylenediisocyanate as the reactants. As blowing agents required for the formation of the foam, the mixtures contain, for example, fluorotrichloromethane or difluorodichloromethane. As an activating additive, the mixtures can additionally contain a tertiary amine such as, for example triethylamine.-

The use of 1 to 15%, preferably %,of the phosphorus-containing flameproofing component, relative to=' the solids content of the reaction mixtures for themanufacture of the polyurethane foam, is appropriate.

The phosphorus compounds incorporated into the polyurethane foams result in extremely flameproof' foams.

Furthermore, additions of such phosphorus compounds do not interfere with the process of manufacture of the foams. r

Admittedly, the present phosphorus compounds in part activate the course of the reaction of polyurethane formation, but this influence can be controlled by appropriate metering of the blowing agents and of the activator additives. The mechanical propertiesare alsonot affected by the addition of the phosphorus compounds, in that practically no distortion occurs.

The process can be used for flameproofingboth socalled rigid and soft polyurethane foams. 'Howev'er, the process is preferably employed for flameproofing polyurethane coatings on substrates containing fibres. V

In the examples which follow, parts are parts by weight and percentages are percentages by weight. The relationship of parts by weight to partsby volume is as ofg.toml. p

EXAMPLE 1 164 parts (0.5 mol) of dimethylphosphonopropionic acid a-hydroxy-p,fl,p-trichloroethylamide in 164 parts of dimethylformamide are warmed in a stirred flask of 500 parts by volume capacity, equipped with a reflux condenser and thermometer, to 68 C. internal temperature so as to give a clear solution. Thereafter 59.5 parts (05 mol) of phenylisocyanate are'run in dropwise over the course of 10 minutes at the same temperature; After completion of the dropwise addition the mixture gradually starts to react, in the course of which the temperature rises as far as C. over the course of 15 minutes and thereafter slowly drops again to about 70 C. The mixture is stirred for a further 12 hours at this temperature and the dimethylformamide is subsequently removed in vacuo (boiling point 11 44-47? (1.). 158 parts of dimethylformarnide are recovered. The reaction product which remains is poured out into a porcelain dish and after having solidified completely is comminuted and recrys tallised from 750 parts of a solvent mixture consisting of 500 parts of benzene and 250 parts of petroleum ether of boiling point 50 to 70 C.

parts of a white, powdery substance of melting point 117 to 119 C. are obtained; its elementary analysisand mass spectrum correspond to the formula The dimethylphosphonopropionic acid 'a-hydroxy-fi,fl,

fl-trichloroethylamide which serves as the starting substance can be manufactured as follows:'

90.5 parts (0.5 mol) of 3 (dimethylphosphono)-propionic acid amide and 82.75 parts (0.5 mol) ofchloral hydrate are suspended in parts of benzene in a stirred flask of 500 parts by volume capacity, equipped with a: water separator and refluxcondenser as well as with 2. and are heated to the boiling point of the benzene. Over the course of 3 hours, 10 parts of water;

thermometer,

originating from the chloral hydrate; are collected 'in the water separator. After completion of the separation ofwater, the mixture is treated for a further 15,.hours at;

the refiux temperature. After cooling, the crystalline reaction product which has precipitated is filtered off, rinsed with a little ether and dried.

EXAMPLE 2 65.5 parts (0.2 mol) of dimethylphosphonopropionic acid a hydroxy 8,3,3 trichloroethylamide are dismol) of phenylisocyanate, dissolved, in ume of acetonitrile,

Yield: 78.5 parts (97% of theory); Melting point: 1l4l17 C.

The product corresponds to the Formula 7.

EXAMPLE 3 The procedure described in Example 2 is followed, except that the phenylisocyanate is replaced by 13.0 parts (0.228 mol) of methylisocyanate. After removal of the acetonitrile, 73 parts of a yellow viscous syrup are obtained and are dissolved in 300 parts by volume of water at room temperature. After a short time, a white precipitate forms, which is filtered off. After drying at room temperature, 22 parts of crude product (fraction 1) are obtained. The aqueous filtrate is evaporated in vacuo at 60 C., whereupon a further 45 parts of crude product (fraction H) are obtained. The two fractions are combined and dissolved, with warming, in 100 parts by the volume of benzene, and 10 parts by volume of ether are added, whereupon crystallisation occurs on stirring and cooling in ice. A further 100 parts by volume of ether are added and the suspension is filtered. The filter residue is dried in vacuo at room temperature.

Yield: 61.5 parts (90% of theory) of white powder; Melting point: 79-81 C.

The elementary analysis and the mass spectrum indicate the formula CHaO EXAMPLE 4 After recrystallisation from 110 parts of isopropyl alcohol, 54 parts of white powder, melting point 119-121 C., are obtained; according to elementary analysis and mass spectrum, this material corresponds to the following formula:

(9) Cl-OHa-CHz-O 0 Cl-CHz-CHa-O EXAMPLE The procedure described in Example 2 is followed, except that instead of the phenylisocyanate 35.0 parts (0.228 mol) of m-chlorophenylisocyanate are used.

After completion of the reaction, the insoluble mate rial is filtered OE and the filtrate is freed of acetonitrile in vacuo at 60 C. 55 parts of a waxy product are obtained and are recrystallised from parts of benzene.

Yield: 41 parts of white powder; Melting point: ll8-128 C.

According to the N, Cl and P analysis, the product corresponds to the formula CHrO CHr-CHzC ONHCHNH EXAMPLE 6 The procedure described in Example 2 is followed, except that instead of the dimethylphosphonoamide 71.3 parts (0.2 mol) of 3-diethylphosphonopropionic acid ahydroxy-p,,8,[3-trichloroethylamide are used.

After completion of the reaction, the insoluble material is filtered off and the filtrate is freed of acetonitrile in vacuo at 60 C. 54.5 parts of a white powder (melting point 15l-152 C.), which is already very pure, are obtained. Elementary analysis indicates the formula (11) olnto o I\ olmo om-omoonn-onqmQ bot.

EXAMPLE 7 The procedure described in Example 2 is followed, except that instead of the dimethylphosphonoamide 76.1 parts (0.2 mol) of 3-dialkylphosphonopropionic acid ahydroxy-p,fl,fl-trichloroethylamide are used.

After completion of the reaction the insoluble material is filtered off and the filtrate is freed of acetonitrile in vacuo at 60 C. 88 parts of a yellow, viscous product are obtained, which can be used without further purification.

The product corresponds to the formula The procedure described in Example 2 is followed, except that the phenylisocyanate is replaced by 28.5 parts (0.114 mol) of 4,4'-diphenylmethane-diisocyanate of the formula O G N CH: -N C O After completion of the reaction, the precipitate is filtered oil and is dried in vacuo at 50 C. Sample 2233x 3 tflfi gflfiifi ut 1 Ii Yield: 78 parts of yellowish powder; additive (3)1 (9) Melting point: 167 C., with decomposition. Burning time'seconds (1) The crude product can be used without further purifi- 5 ,3 $;;%ff';;;;,;g; 83 i cation. Foam density, g./l I 39 N, P and Cl analysis indicates the formula 1 Bums awash CH 0 1 o" Co n i, /P\ /I,\I CHiO omcrnc ONE-ZH-HN-Q-CHQ-NH-iH-ENOC-GHaCH, .i 1 oen' Org... ergo.

EXAMPLE 9 so X MP E .1,. I 26.5 parts of the dimethylphosphonopropionic acid ot- A cotton fabric which has already received afiamei phenylamino-fi,,8, 3-trichloroethylamide of the Formula 7, FY00f finish is coated by the f i s ifi h P obtained according to Example 1, 2.65 parts of a higher followlng Polyurethane pl'epafatlonsilt condensed reaction product of naphthalenesulphonic acid l and formaldehyde and 70.85 parts of water are converted Pss e'e awb to a fine dispersion by grinding in the presence of glass Constituents 0 1 2 a 4 5 7 balls at room temperature for T5 hours. This dispersion Product 0mm formula, 1s Incorporated mto a viscose spinning composltion, usmg (7) 5 a gear disc stirrer, in such a way that the content of g; 5 a carboxylic acid amide is 44.8% relative to cellulose. After (10) x 5' spinning and further processing of the "viscose, a textile 5 5 material of very good flameproof character is obtained. 5

Dltlgethlylifofiamldelmethyl ethyl ke-' 8 '8 a 8 8 8 8 8 no, EXAMPLE 10 Thermoplastic polyester-polyurethane resin 30?, strength solution in DMF/ A mixture of 20 g. of a polyol WhlCh reacts slowly, MEK,1:L) w 60 60 so so 50 50 8 g. of fluorotrichloromethane, 21.4 g. of 4,4-diphenylmethanediisocyanate, 0.2 ml. of an activator based on The m f 8-/m.'.x.- amine and 5 g. of the compound of the Formula 8, 9 or After drymg, the coating. is tested for itsfi qP q 10 is stirred for one minute with a simple blade stirrer 5 character accofdlng to DIN 53,9o5-The 1811mm tlmels at 1000 revolutions per minute. Thereafter the foaming 10 Seconds and the Samples l- 9 8 mass is immediately introduced into a tube of 5.5 cm. i l diameter and the reaction is allowed to go to completion for 7111611. l n .T therein. At the same time a foam without the addition f t r ds f 161133; r g of compounds of the Formula 8, 9 or 10 is produced. rmpmmn 1m mnds m i 0 Bums Test of fiameproof character gm. 8 .3 One specimen at a time of size mm. x 30 mm. x 10 g: l 3 I {gig mm. is fixed with the 120 mm. edge at an angle of 45 gm. g :352 to the horizontal and the 30 mm. edge horizontal. 2:::IIIIII: ,7 ,0: 1

The samples are ignited for 5 seconds at the lower f. end by means of a fishtail burner. The following values What is claimed is: I myare found: 1 Phosphonocarboxylic, acid amides of the formula m-o x PM... o

\ 1 T H I:

P on

wherein R denotes methyl or ethyl chloroethyl or allyl, A denotes phenyl or phenyl substituted by chlorine or methyl or A is alkyl or chloroalkyl with at most 4 carbon atoms and Y denotes hydrogen or methyl.

3. Phosphonocarboxylic acid amides according to claim 2, of the formula wherein R is methyl, ethyl, chloroethyl or allyl and Z denotes hydrogen chlorine or methyl.

4. The phosphonopropionic acid amide according to claim 3, of the formula HaC-O O 10 5. The phosphonopropionic acid amide according to claim 3, of the formula CHrCHrC O-NH-EH-NHQ C1: 6. The phosphonopropionic acid amide according to claim 3, of the formula 7. The phosphonopropionic acid amide according to claim 2 of the formula HIO-O References Cited UNITED STATES PATENTS 2/1959 McConnell et a1. 260-943 X 7/1966 Pianka et a1. 260-943 X OTHER REFERENCES Doerken, Chemical Abstracts, vol. 62 (1965) PP. 3943-4.

35 LEWIS GO'ITS, Primary Examiner R. L. RAYMOND, Assistant Examiner US. Cl. X.R. 

